CN113943237B - Chain extender, preparation method and application thereof - Google Patents
Chain extender, preparation method and application thereof Download PDFInfo
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Abstract
A chain extender, which is 2- (3- (2, 3-dihydroxypropyl) thio) propoxyethyl-3- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate GL, and has the structural formula:
the chain extender GL prepared by the invention has excellent toughening effect, the elongation at break of the polyurethane elastomer prepared by the GL reaches 1531.1594%, and the toughness reaches 12.315% MJ/m 2 Repairing for 6 hours at normal temperature, the repairing efficiency reaches 103.62 percent, repairing for 2 hours at 80 ℃, and the repairing efficiency reaches 125.53 percent. The chain extender GL prepared by the invention can be used in combination with other reinforced chain extenders to cooperatively and further improve the tensile strength and toughness of the polyurethane elastomer.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a chain extender, a preparation method and application thereof.
Background
The polymer material has excellent various properties and is widely applied to the fields of aerospace, electronics, machinery and the like, but in the service process, the material performance is reduced due to material damage caused by abrasion, external force factors and the like, so that the service life of the polymer material is reduced. The self-repairing function is to imitate the organism damage self-repairing mechanism to realize self-repairing of micro-cracks in the material, avoid further damage of the material, recover the initial performance of the material, prolong the service life of the material and provide a new method for preventing potential damage.
The existing polymer material with self-repairing property is characterized in that a chain extender with dynamic covalent bonds and dynamic non-covalent bonds is introduced, reversible reaction of certain chemical bonds is promoted to exchange by means of heating and the like by utilizing dynamic covalent bonds of fracture surfaces, and chain segments are connected with each other, so that repeated repairing is realized. However, in practical application, when the polymer material prepared by the existing chain extender is subjected to self-repairing, the problem that the repairing speed is slower and the repairing efficiency is lower exists, so that the polymer material is difficult to meet the requirements in certain fields with higher requirements, for example, the self-repairing can be realized only at room temperature for 12 hours by the chain extender disclosed in patent CN106117486A and the polyurethane elastomer prepared by the prepolymer, and the repairing efficiency is 75 percent. Therefore, the preparation of the chain extender capable of improving the repair rate and the repair efficiency of the polyurethane elastomer has profound significance.
Disclosure of Invention
The invention aims to provide a chain extender which can effectively improve the self-repairing performance of a polymer and realize the purpose of quick repairing.
Another object of the present invention is to provide a process for preparing the above chain extender.
It is a third object of the present invention to provide the use of the chain extender described above.
The invention aims at realizing the following technical scheme:
a chain extender, characterized in that: the chain extender is 2- (3- (2, 3-dihydroxypropyl) thio) propoxyethyl-3- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate GL, and the structural formula is as follows:
the preparation method of the chain extender GL is characterized by comprising the following steps: mixing 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid AC, ethylene glycol monoallyl ether, cyclohexane and p-toluenesulfonic acid in N 2 Preparation of solid product ES (2- (allyloxy) ethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate) by reflux reaction under atmosphereThe solid product ES is mixed with 2, 2-dimethoxy-2-phenyl acetophenone, tetrahydrofuran and 1-thioglycerol for ultraviolet irradiation, and the product GL is obtained.
Further, the above AC was prepared by dissolving triethylene glycol bis (3- (3-tert-butyl-4-hydroxy-5-methylphenyl)) propionate AO-70 and NaOH in distilled water, and mixing with N 2 Reflux for 6-8 h under atmosphere, extracting, precipitating and drying.
Further, the dosage ratio of AO-70, naOH and distilled water is 0.1 mol:0.8-1.2 mol:260-270 mL.
Further, the above precipitate was obtained by dropping hydrochloric acid to the extracted solution until the pH became 3 to give a white precipitate suspension, standing for 12 hours, and collecting the precipitate by filtration.
Further, the above-mentioned preparation of solid product ES is specifically carried out by mixing AC and ethylene glycol monoallyl ether, dispersing into cyclohexane, adding p-toluenesulfonic acid, adding into N 2 Reflux reaction is carried out for 6 to 8 hours under atmosphere.
Further, the dosage ratio of the AC to the ethylene glycol monoallyl ether to the cyclohexane is 0.275-0.3 mol:0.25-0.28 mol:150-160 mL, and the dosage of the p-toluenesulfonic acid is 2-2.5 wt% of the ethylene glycol monoallyl ether.
Further, washing the solution obtained by the reaction with saturated sodium bicarbonate solution for 3 times, removing cyclohexane by rotary evaporation to obtain an oily product, and standing at room temperature for 48 hours to obtain a solid product 2- (allyloxy) ethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ES;
further, the ultraviolet irradiation is to mix ES with 2, 2-dimethoxy-2-phenylacetophenone and tetrahydrofuran and continuously charge N 2 10min, adding 1-thioglycerol, mixing, and performing irradiation reaction by adopting 365nm ultraviolet light for 25-40 min.
Further, the ratio of the amount of ES, 1-thioglycerol and tetrahydrofuran is 0.05 mol:0.04-0.06 mol:40-50 mL, and the amount of 2, 2-dimethoxy-2-phenylacetophenone is 0.5-0.6wt% of ES
The most specific method for preparing the chain extender is characterized by comprising the following steps:
(1) Mixing AO-70 and NaOH, dissolving in distilled water, and mixingN 2 Reflux is carried out for 6 to 8 hours under atmosphere, dichloromethane is used for extraction for 2 times, hydrochloric acid is used for titration until the pH value is 3 to generate white precipitate suspension, the white precipitate suspension is kept stand for 12 hours, then the precipitate is filtered and collected, washed to be neutral, and 3- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionic acid AC is obtained after drying, wherein the dosage ratio of AO-70, naOH and distilled water is 0.1mol:0.8 to 1.2mol:260 to 270mL;
(2) Dispersing the mixture of AC and ethylene glycol monoallyl ether into cyclohexane, adding p-toluene sulfonic acid, and adding the mixture into N 2 Reflux reaction for 6-8 h in atmosphere, washing the reacted solution with saturated sodium bicarbonate solution for 3 times, removing cyclohexane by rotary evaporation to obtain oily product, standing at room temperature for 48h to obtain solid product 2- (allyloxy) ethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ES, wherein the dosage ratio of AC, ethylene glycol monoallyl ether and cyclohexane is 0.275-0.3 mol:0.25-0.28 mol:150-160 mL, and the dosage of p-toluenesulfonic acid is 2-2.5 wt% of ethylene glycol monoallyl ether;
(3) Mixing the solid product ES with 2, 2-dimethoxy-2-phenylacetophenone and tetrahydrofuran, and charging N 2 Continuously adding 1-thioglycerol for 10min, mixing, carrying out irradiation reaction by adopting ultraviolet light of 365nm for 25-40 min, finally removing tetrahydrofuran by rotary evaporation to obtain oily product, dissolving the oily product in dichloromethane, washing for 5 times by using distilled water, drying by using anhydrous sodium sulfate, standing for 24h, filtering to remove sodium sulfate, removing dichloromethane by rotary evaporation to obtain oily product GL, wherein the dosage ratio of ES, 1-thioglycerol and tetrahydrofuran is 0.05 mol:0.04-0.06 mol:40-50 mL, and the dosage of 2, 2-dimethoxy-2-phenylacetophenone is 0.5-0.6wt% of ES.
The chain extender GL is applied and is characterized in that: the method is applied to the preparation of polyurethane elastomer.
The polymer molecular chain has high diffusion and excellent exchange capacity, and the polymer molecular chain has high hardness, high entanglement and other properties, so that the molecular chain diffusion and exchange are difficult.
The invention has the following technical effects:
the chain extender GL prepared by the invention has excellent toughening effect, the elongation at break of the polyurethane elastomer prepared by the GL reaches 1531.1594 percent, and the toughness reaches 12.315MJ/m 2 Repairing for 6 hours at normal temperature, the repairing efficiency reaches 103.62 percent, repairing for 2 hours at 80 ℃, and the repairing efficiency reaches 125.53 percent.
The chain extender GL prepared by the invention can be used in combination with other reinforced chain extenders to cooperatively and further improve the tensile strength and toughness of the polyurethane elastomer.
Drawings
Fig. 1: the synthetic route of GL of the invention is schematically shown.
Fig. 2: the AC nuclear magnetism hydrogen spectrogram and the infrared spectrogram prepared in the embodiment 3 of the invention.
Fig. 3: the ES nuclear magnetic hydrogen spectrogram and the infrared spectrogram prepared in the embodiment 3 of the invention.
Fig. 4: GL nuclear magnetic hydrogen spectrogram and infrared spectrogram prepared in the embodiment 3 of the invention.
Fig. 5: example 4 nuclear magnetic hydrogen and infrared spectra of polyurethane elastomers prepared using chain extender GL.
Fig. 6: nuclear magnetic hydrogen profile of the chain extender HMIC used in example 5.
Fig. 7: example 5 nuclear magnetic resonance spectroscopy of polyurethane elastomer prepared using chain extender GL.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing disclosure.
Chemical sources used in the present invention:
guanidine carbonate, ethyl acetoacetate, α -acetyl γ -butyrolactone, triethylamine, ethylene glycol monoallyl ether, 1-thioglycerol, 2-dimethoxy-2-acetophenone, hexamethylene diisocyanate, polytetramethylene ether glycol (PTMEG, mn= -1000 g/mol), dibutyl dilaurate (DBTDL) were purchased from alas Ding Huaxue reagent limited. (China). Absolute ethanol, sodium hydroxide, methylene chloride, hydrochloric acid, p-toluene sulfonic acid, cyclohexane, sodium bicarbonate, tetrahydrofuran, anhydrous sodium sulfate, dimethylformamide (DMF) were purchased from chengdoulong chemical company (china). Dicyclohexylmethane 4,4' -diisocyanate (HMDI) is supplied by the company of the chemical industry group of vanning (china). Triethylene glycol bis (3- (3-tert-butyl-4-hydroxy-5-methylphenyl)) propionate AO-70 was obtained from beijing addition aid institute (china).
Example 1
The preparation method of the chain extender GL comprises the following steps:
(1) Mixing AO-70 and NaOH, dissolving in distilled water, adding into N 2 Reflux for 7h under atmosphere, extracting for 2 times with dichloromethane, titrating the solution with hydrochloric acid until the pH value is 3 to generate white precipitate suspension, standing for 12h, filtering and collecting precipitate, washing to neutrality, and drying to obtain 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid AC, wherein the dosage ratio of AO-70, naOH and distilled water is 0.1mol:0.9mol:265mL;
(2) Dispersing the mixture of AC and ethylene glycol monoallyl ether into cyclohexane, adding p-toluene sulfonic acid, and adding the mixture into N 2 Reflux reaction for 7h in atmosphere, washing the reacted solution with saturated sodium bicarbonate solution for 3 times, removing cyclohexane by rotary evaporation to obtain an oily product, and standing at room temperature for 48h to obtain a solid product 2- (allyloxy) ethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ES, wherein the dosage ratio of AC, ethylene glycol monoallyl ether and cyclohexane is 0.275mol:0.26mol:155mL, and the dosage of p-toluenesulfonic acid is 2.3wt% of the ethylene glycol monoallyl ether;
(3) Mixing the solid product ES with 2, 2-dimethoxy-2-phenylacetophenone and tetrahydrofuran, and charging N 2 Continuing for 10min, adding 1-thioglycerol, mixing, performing irradiation reaction with 365nm ultraviolet light for 25min, and spin-evaporating to remove tetrahydrofuran to obtain oily product, and making into oily productDissolving the product in dichloromethane, washing with distilled water for 5 times, drying with anhydrous sodium sulfate, standing for 24h, filtering to remove sodium sulfate, and steaming to remove dichloromethane to obtain oily product GL, wherein the dosage ratio of ES, 1-thioglycerol and tetrahydrofuran is 0.05mol:0.06mol:40mL, and the dosage of 2, 2-dimethoxy-2-phenylacetophenone is 0.5wt% of ES.
Example 2
The preparation method of the chain extender GL comprises the following steps:
(1) Mixing AO-70 and NaOH, dissolving in distilled water, adding into N 2 Reflux for 6h under atmosphere, extracting for 2 times with dichloromethane, titrating the solution with hydrochloric acid until the pH value is 3 to generate white precipitate suspension, standing for 12h, filtering and collecting precipitate, washing to neutrality, and drying to obtain 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid AC, wherein the dosage ratio of AO-70, naOH and distilled water is 0.1mol:1.2mol:270mL;
(2) Dispersing the mixture of AC and ethylene glycol monoallyl ether into cyclohexane, adding p-toluene sulfonic acid, and adding the mixture into N 2 Reflux reaction for 6h in atmosphere, washing the reacted solution with saturated sodium bicarbonate solution for 3 times, removing cyclohexane by rotary evaporation to obtain an oily product, and standing at room temperature for 48h to obtain a solid product 2- (allyloxy) ethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ES, wherein the dosage ratio of AC, ethylene glycol monoallyl ether and cyclohexane is 0.3mol:0.28mol:160mL, and the dosage of p-toluenesulfonic acid is 2.5wt% of the ethylene glycol monoallyl ether;
(3) Mixing the solid product ES with 2, 2-dimethoxy-2-phenylacetophenone and tetrahydrofuran, and charging N 2 Continuously adding 1-thioglycerol for 10min, mixing, performing irradiation reaction with 365nm ultraviolet light for 40min, removing tetrahydrofuran by rotary evaporation to obtain oily product, dissolving the oily product in dichloromethane, washing with distilled water for 5 times, drying with anhydrous sodium sulfate, standing for 24h, filtering to remove sodium sulfate, and removing dichloromethane by rotary evaporation to obtain oily product GL, wherein the dosage ratio of ES, 1-thioglycerol and tetrahydrofuran is 0.05mol:0.04mol:45mL, and the dosage of 2, 2-dimethoxy-2-phenylacetophenone is 0.6wt% of ES.
Example 3
The preparation method of the chain extender GL comprises the following steps:
(1) Mixing AO-70 and NaOH, dissolving in distilled water, adding into N 2 Reflux for 8h under atmosphere, extracting with dichloromethane for 2 times, titrating the solution with hydrochloric acid until the pH value is 3 to generate white precipitate suspension, standing for 12h, filtering and collecting precipitate, washing to neutrality, and drying to obtain 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid AC, wherein the dosage ratio of AO-70, naOH and distilled water is 0.1mol:0.8mol:260mL, and the structural formula of the AC can be determined according to figure 2;
(2) Dispersing the mixture of AC and ethylene glycol monoallyl ether into cyclohexane, adding p-toluene sulfonic acid, and adding the mixture into N 2 Reflux reaction for 8h in atmosphere, washing the reacted solution with saturated sodium bicarbonate solution for 3 times, removing cyclohexane by rotary evaporation to obtain oily product, standing at room temperature for 48h to obtain solid product 2- (allyloxy) ethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ES, wherein the dosage ratio of AC, ethylene glycol monoallyl ether and cyclohexane is 0.275mol:0.25mol:150mL, the dosage of p-toluenesulfonic acid is 2wt% of ethylene glycol monoallyl ether, and the structure of ES can be determined by figure 3;
(3) Mixing the solid product ES with 2, 2-dimethoxy-2-phenylacetophenone and tetrahydrofuran, and charging N 2 Continuously adding 1-thioglycerol for 10min, mixing, performing irradiation reaction with 365nm ultraviolet light for 30min, removing tetrahydrofuran by rotary evaporation to obtain oily product, dissolving the oily product in dichloromethane, washing with distilled water for 5 times, drying with anhydrous sodium sulfate, standing for 24h, filtering to remove sodium sulfate, and removing dichloromethane by rotary evaporation to obtain oily product GL, wherein the dosage ratio of ES, 1-thioglycerol and tetrahydrofuran is 0.05mol:0.06mol:50mL, and the dosage of 2, 2-dimethoxy-2-phenylacetophenone is 0.5wt% of ES.
Structural characterization:
the chain extenders AC, ES, GL prepared in example 3 were dissolved in anhydrous deuterated chloroform, respectively, nuclear magnetic resonance spectra (1 h nmr,400 hz) were recorded on a Bruker Avance III spectrometer (Bruker Daltonics, germany), the nuclear magnetic resonance spectrum of AC was recorded by a fourier infrared spectrometer, the infrared spectrum was recorded by a fourier infrared spectrometer, the nuclear magnetic resonance spectrum of ES was recorded by a fourier infrared spectrometer, the infrared spectrum was recorded by a fourier infrared spectrometer, the nuclear magnetic resonance spectrum of GL was recorded by a fourier infrared spectrometer, and the infrared spectrum was recorded by a fourier infrared spectrometer, as shown in fig. 4 (b). The structural formula is thus determined.
Example 4
The chain extender GL prepared in example 3 is used for preparing polyurethane elastomer, and is specifically carried out according to the following steps:
(1) Drying 20mol Polytetrahydrofuran (PTMEG) with average molecular weight of 1000 at 120deg.C under 60Pa vacuum for 2 hr, cooling to 85deg.C, adding 40mol dicyclohexylmethane 4,4' -diisocyanate (HMDI), and adding N 2 Stirring at 250rpm under atmosphere, reacting for 1h, reducing the temperature to 80 ℃, dropwise adding dibutyl tin dilaurate (DBTDL) accounting for 0.5wt% of polytetrahydrofuran, and adding the mixture into N 2 Continuously stirring and reacting for 3 hours at 250rpm under the atmosphere to obtain a prepolymer;
(2) Adding 20mmol of chain extender GL dissolved in 20mLN, N-Dimethylformamide (DMF) into the prepolymer prepared in the step (1), and continuously stirring at 300rpm for reaction for 3h, wherein the molar volume ratio of GL to DMF is 1-2 mmol/2 mL;
(3) After the reaction, the resulting solution was poured into a mold, allowed to stand at 80℃for curing for 24 hours, and then dried under vacuum at 70 ℃.
The chemical structural formula of the polyurethane elastomer prepared in this example is as follows:
the corresponding nuclear magnetic hydrogen spectrogram is shown in fig. 5 (a), and the infrared spectrogram is shown in fig. 5 (b).
The polyurethane elastomer prepared in the example has a breaking growth rate of 1531.1594 +/-112.2169 and toughness of 12.315 +/-0.122 MJ/m 2 The stress restoration efficiency of 6h restoration at 25 ℃ reaches 103.62% +/-9.59, the stress restoration efficiency of 1h restoration at 80 ℃ reaches 83.47% +/-8.87, and the stress restoration efficiency of 2h restoration is 125.53% +/-9.16. The stress restoration effect described in the inventionThe ratio refers to the ratio of the tensile strength after self-healing to the original tensile strength.
Example 5
Example 3 compounding of chain extender GL and chain extender HMIC for the preparation of polyurethane elastomer, the following steps are specifically performed:
(1) Taking out 20mmol Polytetrahydrofuran (PTMEG) with average molecular weight of 1000, drying at 110deg.C under 40Pa vacuum for 2h, reducing the temperature to 85deg.C, adding 41mmol dicyclohexylmethane 4,4' -diisocyanate (HMDI), and adding N 2 Stirring at 220rpm under atmosphere, reacting for 1h, reducing the temperature to 80 ℃, dropwise adding dibutyl tin dilaurate (DBTDL) accounting for 1wt% of polytetrahydrofuran, and adding the mixture into N 2 Continuously stirring and reacting for 3 hours at 220rpm under the atmosphere to obtain a prepolymer;
(2) Adding 8mmol of solid chain extender HMIC into the prepolymer prepared in the step (1), stirring at 250rpm for reaction for 0.5h, then adding 12mmol of chain extender GL dissolved in 20mLN, N-Dimethylformamide (DMF), and continuing stirring at 250rpm for reaction for 3h;
(3) After the reaction, the resulting solution was poured into a mold, allowed to stand at 80℃for curing for 24 hours, and then dried under vacuum at 70 ℃.
The preparation method of the chain extender HMIC comprises the following steps:
mixing alpha-acetylgamma-butyrolactone, guanidine carbonate and triethylamine according to the dosage ratio of 0.1mol:0.1mol:0.2mol:100mL, carrying out reflux reaction for 20h, carrying out vacuum suction filtration to obtain a yellow solid crude product after the reaction is finished, washing the crude product with absolute ethyl alcohol, dissolving the crude product in distilled water to form a suspension, adjusting the pH value to 7, carrying out vacuum suction filtration, and drying to obtain a white solid product HMIC.
The chemical structure of the HMIC prepared is as follows:
The chemical structure of the polyurethane elastomer prepared in this example is as follows:
the corresponding nuclear magnetic hydrogen spectrum is shown in figure 7.
The polyurethane elastomer has a fracture growth rate of 2042.6293 percent+/-122.0326 and toughness of 144.142 +/-7.7 MJ/m 2 The notch breaking energy is 13.624 +/-0.165 KJ/m 2 The stress restoration efficiency of the polyurethane elastomer for 3h restoration at 80 ℃ is 81.16 +/-1.29, the stress restoration efficiency of the polyurethane elastomer for 6h restoration at 80 ℃ reaches 93.18+/-1.82, the elongation at break of the polyurethane elastomer prepared by using the chain extender HMIC alone is only 148.3576 +/-37.0352, the toughness is 42.692 +/-6.722, and the notch breaking energy is 2.374 +/-0.271 KJ/m 2 Repairing for 6 hours at 80 ℃, wherein the stress repairing efficiency is only 39.54% +/-1.26.
The polyurethane elastomer prepared in this example was shaped to stretch a 0.7mm thick specimen to 650% elongation, recovering almost completely from 650% elongation in 30 seconds, and the 0.7mm thick specimen was not even pierced until the elongation reached 500%. PU-HM-HP has good recovery from repeated deformation and excellent puncture resistance.
Claims (10)
1. A chain extender, characterized in that: the chain extender is 2- (3- (2, 3-dihydroxypropyl) thio) propoxyethyl-3- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate GL, and the structural formula is as follows:
2. the method of preparing a chain extender of claim 1, wherein: mixing 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid AC, ethylene glycol monoallyl ether, cyclohexane and p-toluenesulfonic acid in N 2 And (3) carrying out reflux reaction under atmosphere to prepare a solid product ES, mixing the solid product ES with 2, 2-dimethoxy-2-phenylacetophenone, tetrahydrofuran and 1-thioglycerol, and carrying out ultraviolet irradiation to obtain a product GL.
3. The method of preparing a chain extender of claim 2, wherein: the AC is prepared by mixing triethylene glycol bis (3- (3-tertiary butyl-4-hydroxy-5-methylphenyl)) propionate AO-70 and NaOH, dissolving in distilled water, and adding the mixture into N 2 Reflux for 6-8 h under atmosphere, extracting, precipitating and drying.
4. A process for the preparation of a chain extender as claimed in claim 2 or claim 3 wherein: the reflux reaction to prepare solid product ES is carried out by dispersing AC and ethylene glycol monoallyl ether mixture into cyclohexane, adding into p-toluene sulfonic acid, adding into N 2 Reflux reaction is carried out for 6 to 8 hours under atmosphere.
5. The method for preparing the chain extender as claimed in claim 4, wherein: the dosage ratio of the AC, the ethylene glycol monoallyl ether and the cyclohexane is 0.275-0.3 mol:0.25-0.28 mol:150-160 mL, and the dosage of the p-toluenesulfonic acid is 2-2.5 wt% of the ethylene glycol monoallyl ether.
6. The method for preparing the chain extender as claimed in claim 5, wherein: washing the solution obtained by the reflux reaction with saturated sodium bicarbonate solution for 3 times, removing cyclohexane by rotary evaporation to obtain an oily product, and standing at room temperature for 48 hours to obtain a solid product, namely 2- (allyloxy) ethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ES.
7. The method of preparing a chain extender as claimed in claim 6 wherein: the ultraviolet irradiation is to mix ES with 2, 2-dimethoxy-2-phenyl acetophenone and tetrahydrofuran and then charge N 2 Continuing for 10min, adding 1-thioglycerol, mixing, and carrying out irradiation reaction by adopting 365nm ultraviolet light for 25-40 min.
8. The method of preparing a chain extender of claim 7, wherein: the dosage ratio of the ES, the 1-thioglycerol and the tetrahydrofuran is 0.05 mol:0.04-0.06 mol:40-50 mL, and the dosage of the 2, 2-dimethoxy-2-phenylacetophenone is 0.5-0.6wt% of the ES.
9. A process for the preparation of a chain extender as claimed in claim 3 wherein the steps of:
(1) Mixing AO-70 and NaOH, dissolving in distilled water, adding into N 2 Reflux is carried out for 6 to 8 hours under the atmosphere, dichloromethane is used for extraction for 2 times, hydrochloric acid is used for titrating the solution to generate white precipitate suspension, the white precipitate suspension is kept stand for 12 hours, and then the precipitate is filtered and collected, washed to be neutral, and dried to obtain 3- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionic acid AC;
(2) Dispersing the mixture of AC and ethylene glycol monoallyl ether into cyclohexane, adding p-toluene sulfonic acid, and adding the mixture into N 2 Reflux reaction for 6-8 h in atmosphere, washing the reacted solution with saturated sodium bicarbonate solution for 3 times, removing cyclohexane by rotary evaporation to obtain oily product, standing at room temperature for 48h to obtain solid product 2- (allyloxy) ethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ES, wherein the dosage ratio of AC, ethylene glycol monoallyl ether and cyclohexane is 0.275-0.3 mol:0.25-0.28 mol:150-60 mL, and the dosage of p-toluenesulfonic acid is 2-2.5 wt% of ethylene glycol monoallyl ether;
(3) Mixing the solid product ES with 2, 2-dimethoxy-2-phenylacetophenone and tetrahydrofuran, and charging N 2 Continuously adding 1-thioglycerol for 10min, mixing, carrying out irradiation reaction by adopting ultraviolet light of 365nm for 25-40 min, finally removing tetrahydrofuran by rotary evaporation to obtain oily product, dissolving the oily product in dichloromethane, washing for 5 times by using distilled water, drying by using anhydrous sodium sulfate, standing for 24h, filtering to remove sodium sulfate, removing dichloromethane by rotary evaporation to obtain oily product GL, wherein the dosage ratio of ES, 1-thioglycerol and tetrahydrofuran is 0.05 mol:0.04-0.06 mol:40-50 mL, and the dosage of 2, 2-dimethoxy-2-phenylacetophenone is 0.5-0.6wt% of ES.
10. The use of a chain extender as claimed in claim 1 for the preparation of polyurethane elastomers.
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| US10370266B2 (en) * | 2016-05-24 | 2019-08-06 | King Fahd University Of Petroleum And Minerals | Cross-linked polymeric resin and methods for wastewater treatment |
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| GB1341418A (en) * | 1970-08-22 | 1973-12-19 | Bayer Ag | High molecular weight segmented polyurethane elastomers |
| US6521164B1 (en) * | 1996-02-06 | 2003-02-18 | Parker-Hannifin Corporation | Injection-moldable thermoplastic polyurethane elastomer |
| CN107325256A (en) * | 2017-08-04 | 2017-11-07 | 中国科学院过程工程研究所 | Self-healing polymers material and preparation method thereof |
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